Secondary reagent ions

Typical alkylation reactions are those of propane, isobutane, and n-butane by the ferf-butyl or sw-butyl ion. These systems are somewhat interconvertible by competing hydride transfer and rearrangement of the carbenium ions. The reactions were carried out using alkyl carbenium ion hexafluoroantimonate salts prepared from the corresponding halides and antimony pentafluoride in sulfuryl chloride fluoride solution and treating them in the same solvent with alkanes. The reagents were mixed at —78°C warmed up to — 20°C and quenched with ice water before analysis. The intermolecular hydride transfer between tertiary and secondary carbenium ions and alkanes is generally much faster than the alkylation reaction. Consequently, the alkylation products are also those derived from the new alkanes and carbenium ions formed in the hydride transfer reaction. 

Structural features not revealed by El spectra. The ionisation chamber in a Cl source is a gas-tight design allowing pressures in the order of 1 torr to be maintained. The sample molecules and a reagent gas (usually methane or isobutane) up to 10 times in excess is introduced into the ionisation region where it is ionised by the electrons. A secondary ion-molecule reaction then occurs between the sample molecules in low abundance and the primary reagent ions, the resulting secondary ions proceed to the mass analyser. 

Thus, ETD lends the capabilities of ECD to linear ion trap mass spectrometers. The individual steps involved in the operation of an LTQ instrument in ETD mode (Fig. 9.39) are injection of multiply protonated peptides as delivered by an ESI source application of a DC offset to store these ions in the front section of the LIT followed by injection of reagent anions from the Cl source into the center of the LIT. Then all but the peptide precursor ions and the electron-donor reagent ions are ejecteeL Next the DC potential well is switched off and a secondary RF voltage is applied to the end lens plates of the LIT causing positive and negative ion populations to mix and react. The reaction period is ended by axial ejection of reagent anions while positive product ions are retained in the center section of the LIT. Finally, mass-selective radial ejection as usual yields the ETD spectrum [160]. The attractive ETD technique has also been implemented on LITs with axial ejection [144,166] and on LIT-orbitrap hybrids [167-169]. 

Much of the energy deposited in a sample by a laser pulse or beam ablates as neutral material and not ions. Ordinarily, the neutral substances are simply pumped away, and the ions are analyzed by the mass spectrometer. To increase the number of ions formed, there is often a second ion source to produce ions from the neutral materials, thereby enhancing the total ion yield. This secondary or additional mode of ionization can be effected by electrons (electron ionization, El), reagent gases (chemical ionization. Cl), a plasma torch, or even a second laser pulse. The additional ionization is often organized as a pulse (electrons, reagent gas, or laser) that follows very shortly after the... 

Saturated solutions of some reagents (T) 829 Schoniger oxygen flask see Oxygen flask Schwarzenbach classification 53 Screened indicators 268 Sebacic acid 469 Secondary pH standards 831 Selective ion meters 567 Selectivity coefficient, 559 in EDTA titrations, 312 in fluorimetry, 733 of analytical methods, 12 Selenium, D. of as element, (g) 465 Semi-log graph paper 572 Sensitivity (fl) 834, (fu) 732 Separation coefficient 163, 196 Separations by chromatographic methods, 13, 208. 233, 249... 

To determine secondary alkanesulfonates in sewage wastewaters, solid phase extraction (SPE) and a single-step procedure which combines elution and injection port derivatization for analysis with GC-MS were developed [36]. Again a tetrabutylammonium ion pair reagent was employed both to elute the secondary alkanesulfonates as their ion pairs from CI8-bonded silica disks and to derivatize sulfonate ion pairs under GC injection port conditions. Secondary alkanesulfonates were effectively recovered from samples of raw sewage (>92%) and from primary (>98%) and secondary (>85%) effluents. No... 

Dichromate oxidation of secondary alcohols produces ketones in good yield, with little additional oxidation. For example, CH,CH2CH(OH)CH3 can be oxidized to CH CH2COCH3. The difference between the ease of oxidation of aldehydes and that of ketones is used to distinguish them. Aldehydes can reduce silver ions to form a silver mirror—a coating of silver on test-tube walls—with Tollens reagent, a solution of Ag1" ions in aqueous ammonia (Fig. 19.3) ... 

Still another method for the conversion of halides to acid derivatives makes use of Na2Fe(CO>4. As described in 10-112, primary and secondary alkyl halides and tosylates react with this reagent to give the ion RFefCO) (142) or, if CO is present, the ion RCOFe(CO)4 (143). Treatment of 142 or 143 with oxygen or sodium hypochlorite gives, after hydrolysis, a carboxylic acid. " Alternatively, 142 or 143... 

We begin by analyzing the reagent. The methoxide ion is both a strong base and a strong nucleophile. Next, we move on to Step 2 and we analyze the substrate. In this case, the substrate is secondary, so we would expect E2 and Sn2 pathways to compete with each other ... 

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